Bis (phenyltolyl) ether chromatographic adsorption media



United States Patent 3,189,55$ BEQQHENYLTGL DE HER CBRQMATCGRAPHIC ADSQRTTEGN REE JIA James 23. Boedens, 2t! Rosemary Court, Midland, Howard P. Cordts, 5448 Kaserneyer Road, Bay City, and David F. Wisniewsxi, 4869 Franklin St, Auburn, Mich.

N0 Drawing. Original appiication Aug, 31, 1959, Ser. No. 836,927. Divided and this application June 3, 1964, Ser. No. 378,481 7 3 Claims. (Cl. 252-428) This application is a division of U.S. patent application Serial No. 836,927, filed August 31, 1959.

This invention concerns new chemical compositions which are liquid condensation products of a benzenoid hydrocarbon havin up to two alkyl substituents containing from 1 to 2 carbon atoms with 4,4'-di(chl0romethyl)diphenyl oxide, hereinafter abbreviated as DCMDPO It also concerns their method of manufacture.

The new compounds of this invention are unusually effective as adsorbents in chromatography, particularly vapor phase chromatography.

The products of this invention are prepared by a condensation or alkylation in the presence of a Friedel-Crafts catalyst, e.g., ZnCl FeCl 81%, etc., involving two moles of benzenoid hydrocarbon per mole of DCMDPO when the dialkyl benzenes are coreactants, 3 moles of benzenoid hydrocarbon per two moles of DCMDPO when benzene is the coreactant and a mixed condensate of 2 and 3 moles of benzencid hydrocarbon per 1 and 2 moles of DCMDPO when a monoalkylbenzene is the coreactant. For example, bis(ct-x-xylyl-p-tolyl)ether is produced when 2 molar proportions of xylene are condensed with one mole of DCMDPO, x representing a position on the benzene nucleus, u,oz'-biS( (p-(u-phenyl-p-tolyloxy)phenyl) p-xylene is produced when 3 moles of benzene are condensed with 2 moles of DCMDPO, a mixture of approximately 70 weight percent of bis(otx-tolyl-p-tolyl)ether and approximately percent 2-methyl-1,4-bis((p-(a-xtolyl-p-tolyloxy)benzyl)) benzene is produced when toluene present in excess is condensed with DCMDPO, and a mixture of the analogous ethyl homologs, approximately 70 weight percent bis(ct-x-ethylphenyl-p-tolyl)ether and approximately 30 percent 2-ethyl-1,4-bis((p(a-x-ethyl phenyl-p-tolyloxy)benzyl)) benzene is produced when ethylbenzene present in excess is condensed with DCMIWO. The ethylbenzene and toluene condensation products have mainly para-substitution with a small amount of ortho-substitution. The xylene condensate has mainly 1,2,4-substitution with a small amount of 1,2, 3- and 1,2,6-substitution. The indicated positions are those of the alkyl substituents of the beuzenoid hydrocarbon moieties relative to the 4,4'-dimethylene diphenyl oxide moieties, hereinafter referred to as diphenyl oxide moieties.

The reaction is carried out by reacting the benzenoid hydrocarbon, present in stoichiometric excess over the DCMDPO, e.g., more than 2 moles of the former to one of the latter, and sufiicient in any event to dissolve all of the DCMDPO at reaction temperature in the presence of a small catalytic amount of a Friedel-Crafts catalyst, generally from a trace up to 2 weight percent, DCMDPO basis. A simple trial suthces to determine the amount of benzenoid hydrocarbon sufiicient to dissolve the DCMDPO. A reaction temperature between C. and the boiling point of the benzenoid hydrocarbon, generally between and 150 C. and preferably at the boiling point of the benzenoid hydrocarbon reactant is used. Excess benzenoid hydrocarbon acts as a moderating diluent, also expedites reaction in accordance with Le Chatel atented June 15, 1965 ice liers Law and, further, presents self-condensation of the DCMDPO. The reaction is carried out until hydrogen chloride evolution has stopped. At lower temperatures, as expected, longer reaction times are required. But no effect on yield is noted at any point within the operable reaction temperature range provided sufficient time is allowed for all of the hydrogen chloride to be evolved.

The liquid products referred to herein were identified by infrared analysis together with molecular weight determinations.

The DCMDPO can be prepared'by the method of Tomita et 211., ll. Pharm. Soc. lap. 70:44 (1950).

The following examples are in illustration of the invention and not in limitation thereof. Parts and percentages therein are by weight.

EXAMPLE 1.--REACTION OF DCMDPO WITH XYLENE Charge:

107 g. (0.4 mol) DCMDPO 856 g. (8.07 mol) xylene 4 g. zinc chloride The above reactants were charged to a '2-liter 3-necked pot equipped with a mechanically driven agitator and two reflux condensers. Heat was applied gradually to 74 C., at which temperature HCl was evolved vigorously. When the HCl evolution had slowed down, the temperature was increased to 135 C. and was held there for 10 hours. The reaction mixture was then cooled and transferred to a separatory funnel where it was washed twice with water, once with aqueous 5 percent Nail-K30 solution, and again with water. After the final separation, the mixture Was filtered and stripped to 120 C. at 25 mm. Hg to rid it of xylene. The residue was then transferred to another still and stripped of solvent to a pot temperature of 270 C. at 0.7 mm. Hg. A quantity of 127 g. liquid product was recovered for a 79.5 percent yield, DCMDPO basis, identified as bis(a-x-xylyl-p-tolyl)ether by infrared analysis and a molecular weight of 400 (caicd. 406).

EXAMPLE 2.REACTION OF DCMDPO WITH ETHYLBENZENE Charge:

107 g. (0.4 mole) DCMDPO 862 g. (8.07 mole) ethylbenzene 4 g. zinc chloride The procedure of Example 1 was repeated. The washed, filtered organic phase was stripped to 250 C. at 0.7 mm. Hg to remove ethylbenzene. A quantity of g. liquid product was recovered for a 71 percent yield. It was identified as a mixture of approximately 70 weight percent bis(a-x-ethylphenyl-p-tolyl)ether and approximately 30 percent 2 ethyl-1,4-bis( (p-(ot-x-ethylphenyl-p-tolyloxy)- benzyl)) benzene by infrared analysis and a molecular weight of 500 (calcd. for 70:30 mixture, 497).

EXAMPLE 3.REACTION OF DCMDPO WITH TOLUENE A quantity of DCMDPO (534 g., 2 moles) dissolved in toluene (1732 g., 18.8 moles) containing 20 g. zinc chloride was added to a 3-liter 3-necked round bottomed flask equipped with a mechanical agitator, reflux condenser, and thermometer. It was heated with agitation at reflux of the toluene for 2 hours. During the reaction time, HCl was vented through the reflux condenser and a scrubber. The reaction mixture was cooled to 25 -30 C. with agitation. It was then washed three times with an equal volume of cold Water, once with aqueous 5 percent sodium bicarbonate solution, and again with water until the aqueous phase was neutral. The excess toluene and any water was stripped off at a temperature of 250 C. at 2 mm. Hg. Liquid product amounting to 690 g.

was identified as a mixture of ca. 70 Weight percent bis- (u-x-tolyl-p-tolyl) ether and ca. 30 percentZ-methyl-lA- bis((p-(m-x-tolyl-p-tolyloxy)benzyl)) benzene by infrared analysis and by a molecular weight of 458 (calculated of 629 g. liquid product was recovered for a 96.1 percent yield based on DCMDPO. Theproduct was identified as cz,a'-biS( (p- (a-phenyl p-tolyloxy) phenyl) )-p-Xylene by in frared analysis and by a molecular weight of 611 (calcufor 70:30mixture, 462).v lated 620).

EXAMPLE 4.REACTION OFDCMDPO EXAMPLE 5 r WITH BENZENE "The following table illustrates. the value in adsorption V V chromatography of a mixture of about 70 Weight percent A quantity of 1.87 ml. (500 g.) DCMDPO Was dis- 'of bis(m-x-tolyl-p-tclyl). ether and'about 30 weight per solved in 1500 g. (19.2 moles) benzene. To this solut f 2- th 1-1,4-bi 4o1y1- -t 1 1 )b z l) tion Was add d 30 5 alum n m Ch c ly The benzene loaded on a column of diatomaceous earth, a con act ion miXtHr Was at d to reflux in a 61 3- d ventional particulate inert packing material. -In general, the flask equipped with a reflux condenser, th rmometer and data are presented similarlyto' the presentation of Scholly mechanical agitator. .The reaction mixture was held at and Brenner, Proceedings 1959, 2nd Biannual Interna- 60-65 C. for 2 hours, after which no more HCl evolutional Gas Chromatography Symposium, pp. 111-440.

tion was noted. It was then cooled to 50 C. and poured into chilled Water. The organic layer was separated. washed with water, with aqueous 5 percent NaI-ICO burgh ZZjIPa), 1959, except that instead of. giving thetime in minutes for a component species to emerge, there is Instrument So'ciety of America, 313 Sixth Avenue, Pittssolution and again with water. The benzene was then 7 givcnthe retention volume, R o f the ,gas corrected to stripped off to a pot temperature of 200 C. 'A quantity 760 mm. and 0 c.

T able I [Rv values at various temperatures] Compound 13.1. C C.) Temp. 3., (ml./ R /P...

min. cart.) I (penta'ne) Saturated parafiins: 7

Pentane 36.1 99.7 49 09 24. 7 280 1.00 Hexane n 68. 7 99. 7 102 2, 09 3 79. 7 165 2. 28 Heptane- 98. 4 99. 7 212 4, 32 79. 7 371 5. 12 Octane 125. 7 99. 7 406 8, 35 Unsaturated and branched parafiius:

Tentene-l 30.0 99. 7' 51 1 4 24. 7 322 1. 16 cis-Pentene-2 1 36. 9 99. 7 64 1. 31- 2-methyl butane 27. 9 99. 7 35 0, 711

- 24. 7 192 0, 69 2-methyl-1-butene 31.2 99.7 1 11 V 24. 7 356 1. 28 2-methYI-L3-butadiene- 34. 1 99. 7 78 V 1. 57 24. 7 .577 2.07 Halogenated parafiins: A

Methylene chloride.; 40. 0 99. 7 170 .3. 45

. V 24. 7 1, 595 5. 77 Chloroform 61. 3 99. 7 332 6, 73 a 79. 7 582 8. 04

Carbon tetrachloride 76. 7 99.7 363 7, 35

79. 7 625 8. 87 Ethylbromide 38. 4 99.7 -140 2, 84 n-Propyllromide 71. 0 99. 7 306 6. 17 iso-Iropylbromide- 59. 4 99. 7 201 4. 08 n-Butylbromide. 101. 6 99. 7' 634 12.9 iso-Butylbromide- 91. 4 99. 7 .468 9. 51 seo-Butylbromide. 91. 2 99. 7 450 9. 18 Alicycli'e hydrocarbons:

.Cyclopentane 49.3 99.7 115. I 2, 35 g 55.8 352 2. -92 Cyclohexane; 80.7 99. 7 247 5. 08 V p 79. 7 V 418. 6. 25 -Methylcyclohexaue- 100. 9 99. 7 371 7. 63' Aromatic:

Benzene (1 99. 7 V 448 9. 20

'79. 7 804 11. 1 7 Toluene 110. 6 99. 7 956 19. 6 79. 7 1, 866 25. 7

Ethylbenzene 136. 2 99. 7 1,823 37. 4

79. 7 4. 370 42. 8 o-Xylone. 144. 4 V 99. 7 2, 500 50. 3 m-Xylene 139. 1 e 99. 7 2, 067. 41. 5 .p-Xylentt. 138. 4 99. 7 1, 984 40. l Heterocyclic:

Thi0phene 84.4 99. 7 586 11.5 79. 7 1, 089 14. 9 1,4-dioxane 101.4 99. 7 820 16. 7 a a 79. 7 1, 566 21. 6

Alcohols:

'Methauol. 64. 7 99. 7 59 1. 20

' V 79.7 -83 1.14 Ethanol 78. 4 99. 7 106 1, 1 7 79. 7 149 2. 05

n-Propanol 97. 2 99. 7 207 4. 25 iso-PropanoL 82. 4 99. 7 114 2, 32 p n-Butanol 118. O 99. 7 447 9.16

iso-Butanol.-. 108. 0 99.7 309 6.32 sec-B utanol- 99. 5 99. 7 253 5. 15 tert-Butanol 82. 9 99. 7 129 2, 68 iso-Amyl alcohol- 132. 0 99. 7 742 15. 1

Table 1Cont1nued Compound B.P. 0.) Temp. Ry (m1./ Rv/Rv min. corr.) (pen ane) Esters:

Ethyl acetate 77. 1 99. 7 5. 61 79. 7 4. 76 n-Propyl acetate 101. 6 99. 7 2

79. 7 9. 63 n-Butyl acetate 126. 1 99. 7 1 141 23. 2 Ketones:

Acetone 56. l 99. 7 1 55. 8 3. 88 Meth'yl ethyl ketone 79. 6 99. 7 D3 79. 7 5. 13 Methyl propyl ketone 102. 4 99. 7 4 Aldehydes:

Acetaldehyde 20. 2 99. 7 1. 45 24, 7 1. 62 Propionaldehyde 48. 8 99. 7 73 55. 8 3. 61 t Butryaldehyde 74. 7 99. 7 4

ers: Diethyl 34. 6 99. 7 5 24. 7 2. Di-nto l 90. 1 99. 7

p py 79. 7 6. 47 Di-n-butyL 142. 4 99. 7 1, 013 2D. 8 Allyl 94. 3 99. 7 44 tion product of 4,4'-di(chloromethyl) diphenyl oxide with a benzenoid hydrocarbon having the formula R R R C H wherein C H represents a benzene moiety and R R and R individually represent one of the group of hydrogen and alkyl groups having from 1 to 2 carbon atoms and at least one of which is hydrogen, said condensation products having from 1 to 2 diphenyl oxide moieties and from 2 to 3 benzenoid hydrocarbon moieties per molecule.

No references cited.

TOBIAS E. LEVOW, Primary Examiner.

UNITED STATES PATENT OFFICE CERTIFICATE OF CORRECTION Patent No. 3,189,558 June 15, 1965 James D. Doedens et a1.

It is hereby certified that error appears in the above numbered patent requiring correction and that the said Letters Patent should read as corrected below.

In the grant, lines 1 and 2, for "James D. Doedens, of Midland, Howard P. Cordts, of Bay City, and David F. Wisniewski, of Auburn, Michigan," read -James D. Doedens, of Midland, Howard P. Cordts, of Bay City, and David F. Wisniewski, of Auburn, Michigan, assignors to The Dow Chemical Company, of Midland, Michigan, a corporation of Delaware, lines 11 and 12, for "James D. Doedens, Howard P. Cordts, and David F. Wisniewski, their heirs" read The Dow Chemical Company, its successors in the heading to the printed specification, lines 4 to 6, for "James D. Doedens, 2O Rosemary Court, Midland, Howard P. Cordts, 5448 Kasemeyer Road, Bay City, and David F. Wisniewski, 4869 Franklin St., Auburn, Mich." read James D. Doedens, Midland, Howard P. Cordts, Bay City, and David F. Wisniewski, Auburn, Mich., assignors to The Dow Chemical Company, Midland, Mich. a corporation of Delaware column 2, line 1, for "presents" read prevents column 4, Table I, third column, line 39 thereof, for "79.7" read 79.9

Signed and sealed this 16th day of November 1965.

(SEAL) Attest:

ERNEST W. SWIDER EDWARD J. BRENNER Attesting Officer Commissioner of Patents 

3. AN IMPROVED CHROMATOGRAPHIC ADSORPTION MEDIUM COMPRISING A MAJOR PROPORTION OF AN INERT PARTICULATE PACKING MATERIAL AND A MINOR PROPORTION OF A LIQUID CONDENSATION PRODUCT OF 4,4''-DI(CHLOROMETHYL)DIPHENYL OXIDE WITH A BENZENOID HYDROCARBON HAVING THE FORMULA 